Disazo-disulfide dyes



- Patented Jan. 17, 1967 United States Patent "ice 35299 04% addedthereto with stirring, the mixture is heated to 70 DISAZODISULFIDE EYESC. and stirred until in solution. The resulting solution Charles G.Jeremias, Newberry, S.C., and Frederick E. Bar-wick Hi, Mount Holly,N.C., assignors to Martin: Marietta Corporation, a corporation ofMaryland No Drawing. Filed Sept. 6, 1963, Ser. No. 307,014

6 Claims. (Cl. 260-160) thereto with stirring; about 13.8 gms. (0.2g.m.w.) of NaNO will be thus added.

One molecular proportiop of the tetrazotized 4:4'-di--aminoi,2'-dii:hlo1 ocfiplienyldisulfide isthen coupled with 'twomolecular proportions of 3-hydroxy;2-naphtlT-'o- The present inventionrelates to dyes, andmore p ar ticularly to azo-disulfide dyes. f

The azo-disulfide dyes of the present invention are 10 particularlycharacterized in that they have the formula Zmaphtho'anisidide and 8 ofNaOH are dissolved in 500 ml. water at 40 C., which is cooled I I to 0C. and 8 gms. (0.2-'g:m'.w".) more of NaOH are 7 added thereto. While.maintaining the solution of 3 -hy- R 'O O drbxy-Z-naphth-o-anisidide at0 0., add thereto gradu wherein R is the radical of an azoic couplingcomponent. The method of the present invention is particularly solutionof tetrazotized 4.4-diamino-2,2-dichlorod1- characterized in thatazo-disulfide dyes of the above forphenyldisulfide m- Stirfor ithlieehours 15 mula may be prepared by tetrazotizing one molficular recoverthe resulting sol1ds by filtration at C., wash proportion of4z4-diamino-2,2-dichlorodiphenyldisulfide and coupling the tetrazotized4:4-diamino-2,2-dichloroh diphenyldisulfide with two molecularproportions of an yleld 1S nearly ihfioretlcal- I azoic couplingcomponent The resulting dyestuff may be used to dye or print e re ultingdyestuffs may be used to dye and print 25 cotton or regeneratedcellulosic textile fibers red, and has cellulosic fabrics, and it hasbeen found that the presence the following formula inorganics, and drythe resulting product at C. The

| OH O OH of the above two chlorine atoms in the dye molecule en-Example 2 hanceathe light fastness of the dye. Thus, the dyes of thepresent invention have substantially better light fastness thancorresponding dyes which do not have the chlorine atoms. For example,the dye of Example 1 below has substantially better light fastness than.the corresponding azo-disulfide dye made by coupling one molecularproportion of tetrazotized 4:4'-diaminodiphenyldisulfide' with twomolecular proportions of 3-hydroxy-2-naphth-oanisidide.

01-1 0 0 CPD d on c1 or on 1 V y moo-O: N=N ss'- N'=N- ryoorn Thefollowing are suitable and illustrative examples Example 3 for makingthe azo-disulfrde dyes of the present invention.

This example is the same as Example 1 above, except that, 68.3 gms. (0.2g.mIw.) of 4-chloro-3-hydroxy-2- naphtho-o-toluidide are substituted forthe 3-hydroxy-2- n-aphth-o-anisidide used in Example 1 above.

The resulting dyestuff may be used to dye or print cotton or regeneratedcellulosic textile fabrics red, and has the following formula Example 11 l on c on;

is cooled to 0 C. and held at that temperature while a slight excess ofNaNO;,,, as shown on KI paper, is added anisidide as follows. 48.6 gms.(0.2 g.m.'w.) of 3'-hydroxyally over a period of one hour, withstirring, the abovethe solids with water at roomtemperature until freeofExample 4 padding an aqueous solution of sodium sulfide reducing agentozs. Na S/ gal. water) at 150 F. onto the fabric; that 35.8 grns. (0.2g.m.w.) of 1-phenyl-3-methyl-5. Steaming the fabric with neutral airfree steam for l min. clone are Substituted for the 3 hydroxy z naphthoo at 2122l5 F.; washing the fabric with water at 150 F.; anisidide usedin Example 1 above. v 5 passing the fabric through an aqueous solutionof oxidiz- The resulting dyestuff may be used to dye or print cotingagent glacial acetic acid and 1 Sodium ton or regenerated cellulosictextile fibers yellow, and has hromate/gal. water) at 140 F.; rinsing;scouring and the following formula drying.

This example is the same as Example 1 above, except Printings may bemade by applying to the fabric a printing paste consisting of 90ozs.'stardi-tragacanth gum thickener, 9 ozs. thiourea reducing agent, 4ozs. diethvlene glycol, 4 ozs. urea, 6 ozs. soda ash, ozs. of a 20aqueous dispersion of the azo-disulfide dyestuff, and enough water tobring the volume of the printing paste to one gallon; drying the fabric;steaming the fabric with neutral air-free steam for 2-10 mins. toreduce'the dye- Example 5 This example is the same as Example 1 above,except that 41.4 grns. (0.2 g.m.w.) of acetoacet-ortho-anisidide aresubstituted for the 3-hydroxy 2-naphth-o-anisidide used in Example 1.

The resulting dyestuff may be used to dye or print cotton or regeneratedcellulosic textile fibers bright greenishyellow, and has the followingformula C1110 OCII stuff; oxidizing the dye 'by'immersing the fabric for15 seconds in a bath containing 1.5 ozs. glacial acetic acid and 1 02;sodium bichromate per gallon of water; rinsing in water; scouring anddrying the fabric.

If desired, conventional sulfur dyes may be advantageously dyed orprinted in combination with the azodisulfide dye, of the presentinvention, to obtain various shades not obtainable with either dye aloneand to achieve economy, by merely substituting sulfur dye for a portionExample 6 3' This example is the same as Example 1 above, except that18.6 gms. (0.2 g.m.w.) of 3-rnethyl-5-pyrazolone are substituted for the3-hydroxy-2-naphth-o-anisidide used in Example 1.

The resulting dyestuff may be used to dye or print cotton or regeneratedcellulosic textile fibers yellow, and has the following formula OH 01 OH40 of the azo-disulfide dye in the above printing pastes or I Y Ipadding compositions. What is claimed is: HN\ N 7 1. An azo dyestuff ofthe formula L N=c-Cir,- oH,o=N I I The azo-disulfide dyes of the presentinvention may C1 C1 be used to d e or print cotton and regeneratedcellulose C textile fibers by the reduction-oxidation method withoutstanding results. For example, dyeings may be made bypadding ontocottonfabric an aqueous dispersion of the 51) wherein R is the radicalof a naphthol, a pyrazolone or azo-disulfide dye (2 02s, dye/gal. water)at 150 F., allow acetoacet ortho-anisidide ,azoic coupling component,and ing pick-up based on fabric weight; drying the fabric; furthercharacterized in that both R groups are the same.

2. The compound of the formula OH OCH;

3. The compound of the formula moo 3,299,046 5 4. The compound of theformula 5. The compound of the formula N=C-CH| 0H.C=N

6. The compound of the formula References Cited by the Examiner UNITEDSTATES PATENTS 1,973,635 9/1934 Lantz 260-160 X FOREIGN PATENTS 559,7843/ 1944 Great Britain.

CHARLES B. PARKER, Primary Examiner.

JOSEPH P. BRUST, Examiner.

R. I. FINNEGAN, D. M. PAPUGA,

Assistant Examiners.

1. AN AZO DYESTUFF OF THE FORMULA